Process for preparing even dyeings on cellulose materials in a long bath



United States Patent 3,202,472 PROCESS FOR PREPARENG EVEN DYEINGS ONCELLULOSE MATERIALS IN A LONG BATH Edwin Baier, Frankfurt am Main,Germany, assignor to Farbwerlre Hoechst Aktieugesellschaft vormalsMeister Lucius & Briining, Franfiurt am Main, Germany, a corporation ofGermany No Drawing. Filed 06. 1, 1963, Ser. No. 312,876 Claims priority,apnlieation Germany, Oct. 3, 1962,

1 Claim. til. 3-542 3,292,472 Patented Aug. 24, 1%65 from anionic groupsand containing tertiary or quaternary ammonium groups, pyridiniumgroups, ternary sulfonium groups or isothiuronium groups which arelinked to the aromatic nucleus of the dyestuii molecules through bridgemembers of the general formula A-R-, in which R represents a saturatedor unsaturated aliphatic or aliphaticaromatic radical which may beinterrupted by one of several hetero-atoms, and A reprsents the group SOor SO -NR, (R' stands of a hydrogen atom or an alkyl or aralkylradical); and, if desired, by subsequently fixing them fast to washingby a treatment with acidbinding agents, advantageously in an aqueousbath at about 40 C. to 100 C.

According to this method dyestuifs of an analogous constitution whichcontain anionic groups instead of the afore-mentioned cationic groups,are not absorbed by cellulose fibers.

Even dyeings are obtained on dyeing cellulose materials with thedyestuffs of the following Formulae 1, 2 and 3.

in a Weakly acid solution without the addition of levelling auxiliaryagents. The dyestuffs are absorbed by the cellulose materials withoutaddition of salts, whereas the corresponding anionic dyestuffs of thefollowing Formulae 4, 5 and 6 N S i practically do not dye the celluloseunder the same conbicarbonate or tri-sodium phosphate at temperatures inditions and yield weak dyeings in a longboth only with the range ofabout 40 C. and 100 C., preferably at the the addition of largequantities of salts. V boiling temperature.

It was surprising that the cationic dyestuffs .(1) to (3), In thecasesin which the dyestufi and the acid-binding prepared according tosimple manufacturing-gmethods 5 agent do not react in such a way thatprecipitations appear from the anionic dyestuffs (4) to (6) having apoor afin the dyebath or that the dyebath is exhausted quantitafinity,yield deepdyeings on cellulose material in a long tively, dyeing andfixing the material until it is fast to bath withoutaddition of salts,which dyeings, effected in washing can also be carried through in onebath. ly' medium, are SimultaneoulY y even. The following examples serveto illustrate the inven- The dyestuffs used may belong to quitedifferent classes, 10 tion, but they are not intended to limit itthereto, the parts for example to the series'ofphthalocyanine-dyestuiis, azoand percentages being by weight unlessotherwise stated dyestuffs or thia'zol-dyestufis which contain theaforeand the relationship of parts by weight to parts by volumementioned cationic groups. Such dyestuifs can be prebeing the same asthat of the kilogram to the liter. pared, for example, bysulfochlorinating the water-insol- E l 1 uble starting dyestuffs atthearomatic rings, condensing xamp e the so obtained dyestuffsulfochlorides with amines of the 10 parts of a cotton yarn are treatedfor 10 minutes at general formula H NRX (R represents an aliphatic, roomtemperature in 300'parts by volume of an aqueous aromatic or mixedaliphatic-aromatic radical which may solution containing per liter 1gram of acetic acid (of be interrupted by hetero-atoms, and X representsan or- 30% strength)l Within 10 minutes 0.05 part of acetic ganic orinorganic acid radical), andreacting the so preacid (of strength) and0.1 part ofthe dyestuif of the pared ester compounds, which are freefrom sulfonic acid formula i e v C2115 OuPc- SOz-NHCHZCH so2-cn,-crr1I-H) lam 4 I 32135 3 groups, (a) with primary or secondary amines ormer- 3 (prepared by the sulfochlor'ination of tetraphenyl-coppercaptansand converting the so obtained secondary or terphthalocyanine,condensation of the so obtained tetratiary amines or thio-ethers by atreatment with acids or phenyl-copper-phthalocyanine trisulfonic acidchloride dimethyl sulfate into the corresponding tertiary or quawith1-amino-ethyl-benzene-4fl-hydroxyethylsulfone sulternary ammoniumcompounds or ternary sulfoniurn comfuric acid ester and reaction of theso prepared condensapounds, or (b) with thiourea or its derivatives intothe tion product with diethyl amine and subsequently with isothiuroniumcompounds, or (c) with pyridine into the hydrochloric acid) dissolved in10 parts by volume of pyridinium compounds, or (d) with tertiary aminesinto water are then added in portions to the aforementioned thequaternary ammonium compounds. 4 solution. Within minutes the dyebath isslowly heated One can also operate in an analogous manner by reactto theboiling temperature, the yarn is then treated for 10 ing dyestuflesters, containing one or several fi-hydroxy- 40 minutes at thistemperature. It is subsequently rinsed in ethyl sulfonic ester groups,according to the 'afore-menthe heat and in the cold and fiinally treatedfor 1 hour at tioned methods of (a), (b), (c) and (d). the boilingtemperature in a sodium carbonate solution of The dyebath is renderedweakly acid, for example, with 3% strength. acetic acid, in order toreduce the affinity for the cellulose An even green dyeing, possessing avery food fastness and toprovide a slow, even absorption of thedyestufi. 4.5 to wet processing, is obtained.

The necessary dyeing temperature may vary in wide limits, for example inthe range of about 20 C. to 100 C. and must be regulated according tothe dyestufi used. The A cotton fabric is dyed according to the methoddenecessary quantity of acid also depends on the dyestuff scribed inExample 1 with the dyestufi of the formula Example 2 used, since theaffinity for cotton varies for the various (prepared by the coupling of2 mols of diazotized 4-aminodyestuffs and is difierently influenced byacids. benzenesulfonyl-aminoethyl chloride with 1 mol of 2,6- Thefastness to water of the dyeings, prepared accordingbis-(aceto-acetylamino)-benzthiazol and subsequent reacto the presentinvention by dyeing the material in a long tion with pyridine).

bath, is very good. The fastness to washing of the dyeings A very evenyellow dyeing is obtained.

prepared according to the present invention can be improved bysubjecting the dyeings to an after-treatment with acid-binding agents,preferably with an aqueous solution 10 parts of a cotton yarn areintroduced into 500 parts of an alkali metal, for example sodiumcarbonate, sodium by volume of an aqueous solution containing 0.15 partExample 3 of acetic acid (of 30% strength) and 0.2 part of the dyestultof the formula parts of a cotton fabric are introduced into 500 parts byvolume of an aqueous solution containing 0.2 part of acetic acid (of 30%strength) and 0.2 part of the dyestuff of the formula (prepared bycoupling 2 mols of diazotized4-aminobenzene-sulfonyl-aminoethyl-isothiuronium chloride with l mol of1,5 bis (acetoacetylamino)-2,4-dimethoxybenzene).

The dyebath is heated within 30 minutes at C. and the fabric is dyed for1 hour at that temperature, 0.6 part of sodium acetate solution of 10%strength being added in portions at intervals of 10 minutes each.

An even yellow dyeing is obtained which can be improved with regard toits fastness to washing by an aftertreatment at the boil with a sodiumcarbonate solution of 2% strength.

Example 5 10 parts of a staple fiber fabric are treated for 1 hour at C.in 200 parts by volume of an aqueous solution containing 0.1 part ofacetic acid (of 30% strength) and 0.3 part of the dyestuft of theformula (prepared by the sulfochlorination of copper-phthalocyanine,reaction of the copper-phthalocyanine trisulfonic acid chloride soobtained with B-aminoethyl thiosulfuric acid, hydrolysis of the soprepared condensation product into the corresponding mercaptan andreaction with dirnethyl sulfate); the fabric is then rinsed, boiled for10 minutes in a tri-sodium phosphate solution of 3% strength, rinsed,acidified, rinsed again and dried.

An even turquoise blue dyeing, possessing a very good fastness to Wetprocessing, is obtained.

If instead of the atom-mentioned dyestulf 0.3 part of the dyestntf ofthe formula is used, a somewhat more greenish turquoise blue evendyeing, possessing good fastness properties, is obtained.

I claim:

A process for producing even dyeings on shaped articles of a materialselected from the group consisting of natural and regenerated cellulosein a long bath, which consists of treating said shaped articles in adilute weakly acid solution at a temperature between about 20 andaorn-o-sos wherein R represents a lower alkyl group, R represents amember of the group consisting of a hydrogen atom, the benzyl group anda lower alkyl group and X represents an acid radical and wherein Rrepresents lower alkyl groups and X is defined as above, which groupsare linked to a carbon atom 'ofran aromatic nucleus of the dyestuffmolecule through a bridge member selected from the group consisting ofwherein R represents a member of the group consisting of a hydrogen atomand an alkyl group, and

,SO CH CH and fixing the dyeings so obtained by treating them with anacid binding agent in an aqueous bath at a temperature between 40 and100 C.

References Cited by the Examiner UNITED STATES PATENTS 3,044,843 7/62Tullio 8--1.214 3,066,005 11/62 Wedemeyer et al 854.2 3,088,790 5/63Sehultheis et a1. 854.2 3,096,340 7/63 Tartter et a1. 81.2l4 3,116,10312/63 Garnlen et a1. 854.2 X

OTHER REFERENCES Du Pont, Technical Information Bulletin R 26, May 1957,p. 15, under Drying.

S.V. F.)Fachorgan, 17, October 1962, pp. 703-707.

NORMAN G. TORCHIN, Primary Examiner.

